Certain 2-(2-substituted benzoyl)-4-(substituted)-1,3-cyclohexanediones

ABSTRACT

Compounds of the formula ##STR1## wherein R is halogen; C 1  -C 2  alkyl; C 1  -C 2  alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C 1  -C 2  haloalkyl; R a  SO n  -- wherein n is 0 or 2 and R a  is C 1  -C 2  alkyl; trifluoromethyl or difluoromethyl; 
     R 1  is hydrogen, C 1  -C 4  alkyl, halogen, phenyl or substituted phenyl; 
     R 2  is hydrogen or C 1  -C 4  alkyl; or 
     R 1  and R 2  together are C 2  -C 5  alkylene; 
     R 3  is hydrogen, C 1  -C 4  alkyl, phenyl or substituted phenyl, with the proviso that R 1  and R 3  are not both phenyl or substituted phenyl; 
     R 4  is hydrogen or C 1  -C 4  alkyl; 
     R 5  is hydrogen, halogen or C 1  -C 4  alkyl; 
     R 6  is halogen, cyano, nitro, trifluoromethyl, --C(O)--OR f  wherein R f  is C 1  -C 4  alkyl, or --C(O)NR 2   b  wherein R b  is hydrogen or C 1  -C 2  alkyl; 
     R 7  and R 8  independently are (1) hydrogen; (2) halogen; (3) C 1  -C 4  alkyl; (4) C 1  -C 4  alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C 1  -C 4  haloalkyl; (9) R b  SO n  -- wherein n is the integer 0, 1 or 2; and R b  is (a) C 1  -C 4  alkyl; (b) C 1  -C 4  alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR c  R d  wherein R c  and R d  independently are hydrogen or C 1  -C 4  alkyl; (11) R e  C(O)-- wherein R e  is C 1  -C 4  alkyl or C 1  -C 4  alkoxy; or (12) --SO 2  NR c  R d  wherein R c  and R d  are as defined; and (13) --N(R c )C(O)R d  wherein R c  and R d  are as defined; and their salts.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No. 086,266, abandoned, filed Aug. 20, 1987; which in turn is a continuation-in-part of application Ser. No. 919,277, abandoned, filed Oct. 16, 1986.

BACKGROUND OF THE INVENTION

European Patent Application Nos. 135,191; 186,118; 186,119; and 186,120 relate to certain herbicidal compounds that can have the following structural formula ##STR2## wherein R through R⁵, R⁷ and R⁸ are substantially as defined below and R^(a) is C₁ -C₄ alkyl.

DESCRIPTION OF THE INVENTION

This invention relates to 2-(2-substituted benzoyl)-4-(substituted)-1,3-cyclohexanediones and their use as herbicides.

One embodiment of this invention is an herbicidal composition comprising an herbicidally active 2-(2-substituted benzoyl)-4-(substituted)-1,3-cyclohexanedione and an inert carrier therefor. The 5- and 6-positions and the 4-position of the 1,3-cyclohexanedione moiety are preferably substituted with groups hereinafter defined, most preferably with halogen or methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.

Also embodied within the scope of this invention are novel compounds having the following structural formula ##STR3## wherein R is halogen, preferably chlorine or bromine; C₁ -C₂ alkyl, preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C₁ -C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) -- wherein n is 0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl, trifluoromethyl or difluoromethyl. Preferably, R is chlorine, bromine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂ alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and

R¹ is hydrogen; C₁ -C₄ alkyl, preferably methyl; halogen; phenyl; or substituted phenyl;

R² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R¹ and R² together are C₂ -C₅ alkylene;

R³ is hydrogen; C₁ -C₄ alkyl, preferably methyl; phenyl; or substituted phenyl, with the proviso that R¹ and R³ are not both phenyl or substituted phenyl;

R⁴ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁵ is hydrogen, halogen or C₁ -C₄ alkyl, preferably methyl;

R⁶ is halogen, nitro, cyano, trifluoromethyl, --C(O)--OR^(f) wherein R^(f) is C₁ -C₄ alkyl, --C(O)NR₂ ^(b) wherein R^(b) is hydrogen or C₁ -C₂ alkyl; and

R⁷ and R⁸ independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein

R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl;

(11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or

(13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.

Preferably R⁷ is in the 3-position. More preferably R⁷ is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄ thioalkyl. Most preferably, R⁷ is hydrogen. Preferably R⁸ is in the 4-position. Most preferably R⁸ is halogen, cyano, trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄ haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkyl groups defined above under C₁ -C₄ alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.

The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR4## wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR5## wherein R, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of this invention that varying degrees of association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.

The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds or their salts to the area where control is desired.

The compounds of the present invention can be prepared by the following two-, or, if necessary, a three-step general method.

The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2), or, if necessary, by subsequent halogenation of the product obtained in step (2) as shown in reaction (3).

The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.

Reactions (1) and (2) may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR6## wherein R through R⁸ and moderate base are as defined and Y is halogen, preferably chlorine, C₁ -C₄ alkyl--C(O)--O--, C₁ -C₄ alkoxy--C(O)--O-- or ##STR7## wherein R, R⁷ and R⁸ in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0° C.-50° C. until the reaction is substantially complete. ##STR8## wherein the moderate base and R through R⁸ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.01-0.1 mole of the cyanide source. The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50° C., preferably about 20° C. to about 40° C., and the desired product is recovered by conventional techniques.

In the alternative, certain compounds of this invention can be prepared by the following reaction: ##STR9## wherein R, R¹, R², R³, R⁴, R⁵, R⁷ and R⁸ are as defined, and R⁶ is halogen.

Generally, in step (3) a mole amount of the 2-(2-substituted benzoyl)-1,3-cyclohexanedione is dissolved in a solvent such as methylene chloride. With proper external cooling, such as a dry ice-isopropanol bath, a 1-3 mole amount of a halogenating agent, such as bromine is added with or without a solvent to produce a compound having 1-3 halogens at positions 4- or 6- on the 1,3-cyclohexanedione moiety. An additional mole of the halogenating agent is used for each additional halogen substituent that is desired. To have the additional halogenation of R¹ or R⁵ these groups must be hydrogen in the precursor compound. The reaction mixture is then stirred at room temperature for 1 to 8 hours. The product is worked up by conventional techniques.

The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.

Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; benzaldehyde cyanohydrin; cyanohydrins of C₂ -C₅ aliphatic aldehydes such as acetaldehyde cyanohydrin, propionaldehyde cyanohydrin, etc.; cyclohexanone cyanohydrin; lactonitrile; zinc cyanide; di- and tri-(lower alkyl) silyl cyanides, notably dimethyl- and trimethylsilyl cyanide; potassium ferric cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.

The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40° C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as N,N-dimethylaniline (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.

A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated product. A preferred solvent for this reason is 1,2dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50° C.

The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR10## wherein R, R⁷ and R⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods described therein. ##STR11## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR12## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR13## wherein R, R⁷ and R⁸ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.

The above-described substituted 1,3-cyclohexanediones can be prepared according to the teachings of Modern Synthetic Reactions, 2nd Edition, Chap. 9, H. O. House, W. A. Benjamin, Inc., Menlo Park, CA (1972) and Von Hans Machleidt and Valentine Hartmann, Liebigs Ann. Chem., 679, 9 (1964).

The following examples teach the synthesis of a representative compound of this invention.

EXAMPLE 1 5,5-dimethyl-4-fluoro-2-(2-nitro-4-trifluoromethylbenzoyl)cyclohexane-1,3-dione triethylamine salt ##STR14##

5,5-Dimethyl-4-fluoro-1,3-cyclohexanedione [0.5 grams (g), 0.0032 mole, prepared according to the teaching of Liebigs Ann. Chem., 679, 9 (1964)] and 0.25 g (0.0032 mole) pyridine were dissolved in 20 milliliters (ml) methylene chloride at room temperature. 2-Nitro-4-trifluoromethylbenzoyl chloride (1.0 g, 0.0039 mole) dissolved in 20 ml methylene chloride was slowly added with cooling. The reaction mixture was stirred at room temperature for 24 hours and then washed two times with water, one time with saturated sodium bicarbonate aqueous solution and one with with water. The aqueous phases were discarded and the organic phase dried with MgSO₄ and then evaporated to yield the intermediate enol ester, 5,5-dimethyl-6-fluoro-3-(2-nitro-4-trifluoromethylbenzoyloxy)cyclohex-2-enone. The 5,5-dimethyl-6-fluoro-3-(2-nitro-4-trifluoromethylbenzoyloxy)cyclohex-2-enone was dissolved in 30 ml acetonitrile and triethylamine (0.7 g, 0.007 mole) which was added all at once, followed by acetonecyanohydrin (0.05 g, 0.0006 mole). The solution was stirred for 24 hours. The solvent was evaporated and the residue washed with diethyl ether to yield the product.

EXAMPLE 2 2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione ##STR15##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole] and 23.3 g (0.1 mole) 2-chloro-4-methanesulfonylbenzoyl chloride was dissolved in 200 ml methylene chloride at room temperature. Triethylamine (11 g, 0.11 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase dried with MgSO₄ and then evaporated to yield the intermediate enol ester 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone. The 3-(2-chloro-4-methanesulfonylbenzoyloxy)cyclohex-2-enone was dissolved in 200 ml acetonitrile and triethylamine (22 g, 0.22 mole) was added all at once, followed by acetonecyanohydrin (0.8 g, 0.01 mole). The solution was stirred for 5 hours and then poured into 2N HCl and extracted twice with ethyl acetate. The organic layer was dried with MgSO₄ and the solvent evaporated to yield the product.

EXAMPLE 3 4-Bromo-2-(2-chloro-4-methanesulfonylbenzoyl)cyclohexane-1,3-dione ##STR16##

2-(2-Chloro-4-methanesulfonylbenzoyl)-cyclohexane-1,3-dione (6.6 g, 0.02 mole) was dissolved in 50 ml of methylene chloride. Bromine (2.9 g, 0.018 mole) dissolved in 50 ml of methylene chloride was added dropwise over a period of 75 minutes to the above solution which was cooled with a dry ice-isopropanol bath. Upon completion of the addition, the reaction mixture was stirred an additional 2 hours at room temperature. The reaction mixture was then concentrated under vacuum to afford 8.5 g of the desired product as a semi-solid. It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy, and mass spectroscopy. The product can be further purified by column chromatography.

The following is a table of certain selected compounds that are preparable according to the procedure described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

                                      TABLE I                                      __________________________________________________________________________      ##STR17##                                                                     Cmpd.                                 Physical Constant                        No. R  R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                           R.sup.4                                                                           R.sup.5                                                                          R.sup.6                                                                             R.sup.7                                                                             R.sup.8                                                                               (m.p. °C.)                        __________________________________________________________________________     .sup.  1.sup.a                                                                     Cl H  H  H  H  H Br   H    4-SO.sub.2 CH.sub.3                                                                   semi-solid                                2  Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Br   H    4-Cl   oil                                       3  Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  Br                                                                               Br   H    4-Cl   oil                                       4  Cl Br H  H  H  H Br   H    4-Cl   oil                                       5  Cl Br H  H  H  H Br   H    4-SO.sub.2 CH.sub.3                                                                   70-85                                     6  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Br   H    H      105-115                                   7  Cl H  H  H  H  H Cl   H    4-Cl   oil                                      .sup.  8.sup.b                                                                     NO.sub.2                                                                          H  H  CH.sub.3                                                                          CH.sub.3                                                                          H F    H    4-CF.sub.3                                                                            128-130                                   9  NO.sub.2                                                                          H  H  CH.sub.3                                                                          CH.sub.3                                                                          H F    H    4-CF.sub.3                                                                            140-144                                  10  Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Br   H    4-SO.sub.2 CH.sub.3                                                                   73-87                                    11  NO.sub.2                                                                          H  H  H  H  H Br   H    4-Cl   145-162                                  12  Cl H  H  H  H  Cl                                                                               Cl   H    4-Cl   oil                                      13  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   H    H      oil                                      .sup. 14.sup.b                                                                     Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   H    4-SO.sub.2 CH.sub.3                                                                   oil                                      15  Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   H    4-SO.sub.2 CH.sub.3                                                                   oil                                      .sup. 16.sup.b                                                                     NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   H    4-SO.sub.2 CH.sub.2 Cl                                                                oil                                      .sup. 17.sup.b                                                                     Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      18  Cl CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      19  NO.sub.2                                                                          CH.sub.3                                                                          CH.sub.3                                                                          H  H  H Cl   H    4-SO.sub.2 CH.sub.2 Cl                                                                oil                                      20  Cl H  H  H  H  Br                                                                               Br   3-Cl 4-Cl   oil                                      21  Cl Br H  H  H  H H    H    4-Cl   oil                                      22  Cl F  H  CH.sub.3                                                                          CH.sub.3                                                                          H H    H    4-SO.sub.2 CH.sub.3                                                                   oil                                      23  NO.sub.2                                                                          H  H  H  H  F CO.sub.2 C.sub.2 H.sub.5                                                            H    H      oil                                      24  NO.sub.2                                                                          Cl H  H  H  H H    H    H      oil                                      .sup. 25.sup.b                                                                     Cl H  H  H  H  F CO.sub.2 C.sub.2 H.sub.5                                                            H    4-SO.sub.2 CH.sub.3                                                                   oil                                      26  Cl F  H  CH.sub.3                                                                          CH.sub.3                                                                          H H    3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      .sup. 27.sup.b                                                                     Cl Cl H  H  H  H H    H    4-SO.sub.2 CH.sub.3                                                                   oil                                      28  Cl Cl H  H  H  H H    H    4-SO.sub.2 CH.sub.3                                                                   oil                                      29  NO.sub.2                                                                          Cl H  H  H  H H    H    4-CF.sub.3                                                                            oil                                      30  NO.sub.2                                                                          F  H  H  H  H H    H    4-CF.sub.3                                                                            oil                                      31  Cl F  H  H  H  H H    H    4-SO.sub.2 CH.sub.3                                                                   oil                                      32  Cl F  H  H  H  H H    3-OC.sub.2 H.sub.5                                                                  4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      .sup. 33.sup.b                                                                     Cl F  H  CH.sub.3                                                                          CH.sub.3                                                                          H H    3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      34  Cl F  H  CH.sub.3                                                                          CH.sub.3                                                                          H H    3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            oil                                      __________________________________________________________________________      .sup.a Prepared in Example 3.                                                  .sup.b Prepared as a triethylamine salt.                                 

HERBICIDAL SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 80° F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.

The results of the tests are shown in the following Table II.

                  TABLE II                                                         ______________________________________                                         Pre-Emergence Herbicidal Activity                                              Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG      WO    AMG   VL    MD   YNG                               ______________________________________                                          1    100     100     30    60    100   100  80                                 2    100     100     100   75    100   100  80                                 3    30      100     20    10    90     80  70                                 4    0       0       0     0     80     50   0                                 5    30      90      0     20    100    80  80                                 6    100     80      70    5     100    0    0                                 7    100     100     20    100   100   100  80                                 8    100     100     100   100   100   100  80                                 9    --      --      --    --    --    --   --                                10    100     100     100   100   100   100  80                                11    100     100     100   100   100   100  80                                12    100     100     10    20    100   100  80                                13    100     100     100   75    100   100  80                                14    100     100     50    100   100   100  80                                15    100     100     80    100   100   100  80                                16    100     100     60    100   100   100  80                                17    100     100     50    100   100   100  80                                18    --      --      --    --    --    --   --                                19    100     100     50    100   10    100  80                                20    0       100     0     0     100   100  30                                21    100     100     20    40    100   100  80                                22    --      --      --    --    --    --   --                                23    --      --      --    --    --    --   --                                24    100     100     100   90    100   100  80                                25    0       25      10    20    100   100  20                                26    --      --      --    --    --    --   --                                27    --      --      --    --    --    --   --                                28    --      --      --    --    --    --   --                                29    100     100     100   100   100   100  80                                30    100     100     100   100   100   100  80                                31    100     100     100   100   100   100  80                                32    100     100     100   100   100   100  80                                33    100     100     100   80    100   100  80                                34    100     100     95    90    100   100  80                                ______________________________________                                          A dash (--) indicates not tested.                                        

Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the seven different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in Table III.

                  TABLE III                                                        ______________________________________                                         Post-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                  Cmpd.                                                                          No.   FT      WG      WO    AMG   VL    MD   YNS                               ______________________________________                                          1    10      50      10    60    80    80   30                                 2    80      100     60    60    95    100  70                                 3    0       10      0     10    80    90   30                                 4    0       0       0     5     90    90   0                                  5    0       75      0     10    80    50   30                                 6    100     90      100   20    100   50   30                                 7    100     100     85    100   100   100  80                                 8    100     100     90    100   90    100  60                                 9    --      --      --    --    --    --   --                                10    100     100     100   85    90    85   30                                11    30      80      20    60    80    80   30                                12    10      100     10    100   100   100  30                                13    90      80      80    60    90    90   30                                14    100     100     85    100   100   100  80                                15    100     100     100   100   100   100  80                                16    100     80      30    100   100   100  80                                17    100     90      30    100   100   100  80                                18    --      --      --    --    --    --   --                                19    100     85      30    95    90    100  60                                20    100     80      0     60    90    100  30                                21    100     100     30    100   100   100  70                                22    --      --      --    --    --    --   --                                23    --      --      --    --    --    --   --                                24    100     100     100   100   100   100  80                                25    0       50      0     60    85    100  0                                 26    --      --      --    --    --    --   --                                27    --      --      --    --    --    --   --                                28    --      --      --    --    --    --   --                                29    100     100     100   100   100   100  90                                30    100     100     100   100   100   100  90                                31    100     100     100   100   100   100  80                                32    100     100     100   100   100   100  80                                33    80      80      80    80    80    100  0                                 34    90      90      90    95    100   100  0                                 ______________________________________                                          A dash (--) indicates not tested.                                        

The compounds of the present invention and their salts are useful as herbiides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable

PRE-EMERGENCE MULTI-WEED HERBICIDE TEST

Several compounds were evaluated at an application rate of 1 lb/acre (1.12 kg/ha) for pre-emergence activity against a larger number of weed species.

The process was generally similar to the pre-emergence herbicide test described above except that only 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

Redroot pigweed (PW) was eliminated in this test and the following weed species were added:

    ______________________________________                                         Grasses:                                                                              downybrome     Bromus tectorum                                                                              (DB)                                              annual ryegrass                                                                               Lolium multiflorum                                                                           (ARG)                                             rox-orange sorghum                                                                            Sorghum bicolor                                                                              (SHC)                                             hemp sesbanis  Sesbania exaltata                                                                            (SESB)                                            nightshade     Solanum sp.   (SP)                                              cocklebur      Xanthium sp.  (CB)                                       ______________________________________                                    

The results of the 1.12 kg/ha test are shown in Table IV.

                                      TABLE IV                                     __________________________________________________________________________     Pre-Emergence Multi-Weed Herbicide Test                                        Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      9  -- 100                                                                               20  100                                                                               100                                                                               70 100                                                                               98   98 100                                                                               95 -- 100                                                                               95                               18  -- 100                                                                               50  100                                                                               70 20 20 100 100 100                                                                                0 --  20                                                                               50                               22  -- 10 20   95                                                                               100                                                                               20 10 90  100 100                                                                                0 -- 100                                                                               25                               23  -- 90 20   90                                                                               75  0  0  0   70  90                                                                                0 --  30                                                                                0                               26  -- 100                                                                               80  100                                                                               95 100                                                                               100                                                                               100 100 100                                                                               75 --  90                                                                               90                               27  -- 65  0  100                                                                               80  0 85 100 100 100                                                                               75 -- 100                                                                               100                              28  -- 95 10  100                                                                               90 20 85 98  100 100                                                                               100                                                                               -- 100                                                                               95                               __________________________________________________________________________      A dash (--) indicates not tested.                                        

POST-EMERGENCE MULTI-WEED HERBICIDE TEST

Several compounds were evaluated at an application rate of 1 lb/acre (1.12 kg/ha) for post-emergence activity against the larger number of weed species that were used in the pre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide test described above except that only 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.

The results of the 1.12 kg/ha test are shown in Table V.

                                      TABLE V                                      __________________________________________________________________________     Post-Emergence Multi-Weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                  Cmpd.                                                                          No. DB FT ARG WG SHC                                                                               WO BSG                                                                               AMG SESB                                                                               VL SP MD YNS                                                                               CB                               __________________________________________________________________________      9  -- 100                                                                               0   100                                                                               95 75 100                                                                               98  100 100                                                                               90 -- 95 100                              18  --  95                                                                               0   100                                                                               70  0  50                                                                               100 100 100                                                                                0 -- 65 --                               22  --  50                                                                               30   95                                                                               50 70 100                                                                               95  100 100                                                                               95 -- 60 --                               23  --  50                                                                               0    20                                                                               25 10  95                                                                               25   95 100                                                                                0 -- 20  30                              26  -- 100                                                                               10  100                                                                               40 100                                                                               100                                                                               98  100  95                                                                               25 -- 10  95                              27  -- 100                                                                               0   100                                                                               100                                                                               20 100                                                                               98  100 100                                                                               20 -- 50 100                              28  -- 100                                                                               0   100                                                                               75 35 100                                                                               100 100 100                                                                               70 -- 40 100                              __________________________________________________________________________      A dash (--) indicates not tested.                                        

The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are preapred to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain from about 0.1 to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as destrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to the conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.

    __________________________________________________________________________     General Formula with Ranges                                                                          Specific Formula                                         __________________________________________________________________________     EMULSIFIABLE CONCENTRATE FORMULATIONS                                          Herbicidal compound                                                                           5-55   herbicidal compound                                                                         24                                          surfactant(s)  5-25   proprietary blend of oil-                                                                   10                                          solvent(s)     20-90  soluble sulfonates and                                                  100%   polyoxyethylene ethers                                                         polar solvent                                                                               27                                                                petroleum hydrocarbon                                                                       39                                                                             100%                                        WETTABLE POWDER FORMULATIONS                                                   herbicidal compound                                                                           3-90   herbicidal compound                                                                         80                                          wetting agent  0.5-2  sodium dialkyl naphthalene                                                                  0.5                                         dispersing agent                                                                              1-8    sulfonate                                                diluent(s)     8.5-87 sodium lignosulfonate                                                                       7                                                          100%   attapulgite clay                                                                            12.5                                                                           100%                                        EXTRUDED GRANULAR FORMULATIONS                                                 herbicidal compound                                                                           1-20   herbicidal compound                                                                         10                                          binding agent  0-10   lignin sulfonate                                                                            5                                           diluent(s)     70-99  calcium carbonate                                                                           85                                                         100%                100%                                        FLOWABLE FORMULATIONS                                                          herbicidal compound                                                                           20-70  herbicidal compound                                                                         45                                          surfactant(s)  1-10   polyoxyethylene ether                                                                       5                                           suspending agent(s)                                                                           0.05-1 attagel      0.05                                        antifreeze agent                                                                              1-10   propylene glycol                                                                            10                                          antimicrobial agent                                                                           1-10   1,2-benzisothiazoline-3-one                                                                 0.03                                        antifoam agent 0.1-1  silicone defoamer                                                                           0.02                                        solvent        7.95-77.85                                                                            water        39.9                                                       100%                100%                                        __________________________________________________________________________

When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.

The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. 

What is claimed is:
 1. Compounds of the formula ##STR18## wherein R is halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C₁ -C₂ haloalkyl; R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl; trifluoromethyl or difluoromethyl;R¹ is hydrogen, C₁ -C₄ alkyl, halogen, or phenyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are C₂ -C₅ alkylene; R³ is hydrogen, C₁ -C₄ alkyl, or phenyl, with the proviso that R¹ and R³ are not both phenyl; R⁴ is hydrogen or C₁ -C₄ alkyl; R⁵ is hydrogen, halogen or C₁ -C₄ alkyl; R⁶ is halogen, cyano, nitro, trifluoromethyl, --C(O)--OR^(f) wherein R^(f) is C₁ -C₄ alkyl, or --C(O)NR₂ ^(b) wherein R^(b) is hydrogen or C₁ -C₂ alkyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; and their salts.
 2. The compounds of claim 1 wherein R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R¹, R², R³, R⁴ and R⁵ are hydrogen or methyl; R⁶ is halogen, R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N--(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 3. The compounds of claim 2 wherein R⁷ and R⁸ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl; ethyl or n-propyl, R^(e) C(O)-- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, and R⁷ is in the 3-position and R⁸ is in the 4-position.
 4. The compounds of claim 2 wherein R⁷ is hydrogen and R⁸ are hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 5. The compound of claim 2 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is bromine; R⁷ is hydrogen; and R⁸ is 4--SO₂ CH₃.
 6. The compound of claim 2 wherein R is chlorine; R¹ is methyl; R² is methyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is bromine; R⁷ is hydrogen and R⁸ is 4--chlorine.
 7. The compound of claim 2 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is methyl; R⁴ is methyl; R⁵ is hydrogen; R⁶ is fluorine; R⁷ is hydrogen and R⁸ is 4-trifluoromethyl.
 8. The compounds of claim 2 wherein R⁷ is hydrogen.
 9. The compounds of claim 3 wherein R⁷ is hydrogen.
 10. An herbicidal composition comprising a 2-(2-substituted benzoyl)-4-(substituted)-1,3-cyclohexanedione compound of the formula ##STR19## wherein R is halogen; C₁ -C₂ alkyl; C₁ -C₂ alkoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; C₁ -C₂ haloalkyl; R^(a) SO_(n) -- wherein n is 0 or 2 and R^(a) is C₁ -C₂ alkyl; trifluoromethyl or difluoromethyl;R¹ is hydrogen, C₁ -C₄ alkyl, halogen, or phenyl; R² is hydrogen or C₁ -C₄ alkyl; or R¹ and R² together are C₂ -C₅ alkylene; R³ is hydrogen, C₁ -C₄ alkyl, or phenyl with the proviso that R¹ and R³ are not both phenyl; R⁴ is hydrogen or C₁ -C₄ alkyl; R⁵ is hydrogen, halogen or C₁ -C₄ alkyl; R⁶ is halogen, cyano, nitro, trifluoromethyl, --C(O)--OR^(f) wherein R^(f) is C₁ -C₄ alkyl, or --C(O)NR₂ ^(b) wherein R^(b) is hydrogen or C₁ -C₂ alkyl; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C;hd 4 alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C₄ alkyl or C₁ -C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; and (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined; or their salts and an inert carrier therefor.
 11. The composition of claim 10 wherein R is chlorine, bromine, methyl, methoxy, nitro, trifluoromethyl or methylsulfonyl; R¹, R², R³, R⁴ and R⁵ are hydrogen or methyl; R⁶ is halogen; R⁷ and R⁸ independently are (1) hydrogen; (2) halogen; (3) C₁ -C₄ alkyl; (4) C₁ -C₄ alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄ haloalkyl; (9) R^(b) SO_(n) -- wherein n is the integer 0, 1 or 2; and R^(b) is (a) C₁ -C₄ alkyl; (b) C₁ -C₄ alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogen or C₁ -C₄ alkyl; (11) R^(e) C(O)-- wherein R^(e) is C₁ -C.sub. 4 alkyl or C₁ -C₄ alkoxy; or (12) SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined; or (13) --N--(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are as defined.
 12. The composition of claim 11 wherein R⁷ and R⁸ are independently are hydrogen; chlorine; fluorine; bromine; methyl; C₁ -C₄ alkoxy; trifluoromethoxy; cyano; nitro; trifluoromethyl; R^(b) SO_(n) -- wherein n is the integer 0 or 2 and R^(b) is methyl, chloromethyl, trifluoromethyl, ethyl, or n-propyl; R^(e) C(O)-- where R^(e) is C₁ -C₄ alkyl; or SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined and R⁷ is in the 3-position and R⁸ is in the 4-position.
 13. The composition of claim 11, wherein R⁷ is hydrogen and R⁸ is hydrogen, chlorine, bromine, fluorine, cyano, trifluoromethyl or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl or C₁ -C₄ haloalkyl.
 14. The composition of claim 11 wherein R is chlorine; R¹ is hydrogen; R² is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is bromine; R⁷ is hydrogen; and R⁸ is 4-SO₂ CH₃.
 15. The composition of claim 11 wherein R is chlorine; R¹ is methyl; R² is methy; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen; R⁶ is bromine; R⁷ is hydrogen; and R⁸ is 4-chlorine.
 16. The composition of claim 11 wherein R is nitro; R¹ is hydrogen; R² is hydrogen; R³ is methy; R⁴ is methyl; R⁵ is hydrogen; R⁶ is fluorine; R⁷ is hydrogen; and R⁸ is 4-trifluoromethyl. 